EP0052319A1 - Process for the preparation of fluorides of perfluorinate sulphonic acids - Google Patents

Process for the preparation of fluorides of perfluorinate sulphonic acids Download PDF

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EP0052319A1
EP0052319A1 EP81109563A EP81109563A EP0052319A1 EP 0052319 A1 EP0052319 A1 EP 0052319A1 EP 81109563 A EP81109563 A EP 81109563A EP 81109563 A EP81109563 A EP 81109563A EP 0052319 A1 EP0052319 A1 EP 0052319A1
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oxygen
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Klaus Dr. Geisler
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/27—Halogenation
    • C25B3/28—Fluorination

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  • the invention relates to perfluorinated sulfonic acid fluorides of the general formula in which X, Y and Z independently of one another represent F, a perfluoroalkyl radical having 1-8 C atoms, in which one or more CF 2 groups can optionally be replaced by oxygen, the oxygen atoms being separated from one another by at least one CF2 group an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical with 5 to 12 carbon atoms, in which one or more CF 2 groups can be replaced by oxygen,
  • X and Y together for an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical in which one or more CF 2 groups can be substituted by oxygen
  • R f independently represents F or a perfluoroalkyl radical having 1 to 3 carbon atoms
  • n and m represent the numbers 0 or 1.
  • the invention further relates to a process for the preparation of said perfluorinated sulfonic acid fluorides.
  • X 'and Y' together for an optionally alkyl-substituted cycloalkyl radical in which one or several CH 2 groups can be substituted by oxygen and R independently represents H or an alkyl radical having 1 to 3 C atoms to be subjected to the electrochemical fluorination.
  • the preferred class of starting compounds of the general formula II are those in which X ', Y' and Z 'for H, X' and Y 'for a short-chain alkyl radical having 1-6 C atoms, in which a maximum of two CH 2 - Groups are substituted by oxygen or X 'and Y' together represent an optionally alkyl-substituted cycloalkyl radical with 5-8 carbon atoms, where individual CH 2 groups can be replaced by oxygen, and R independently represents H or a methyl group.
  • Examples of the starting compounds used in the process according to the invention are 3-methoxy tetrahydrothiophene-1,1-dioxide, 3-ethoxy-tetrahydrothiophene-1,1-dioxide, 3-n-propoxy-tetrahydrothiophene-1,1-dioxide, 3-i-propoxy-tetrahydrothiophene-1,1-dioxide, 3-n-butoxy-tetrahydrothiophene-1,1-dioxide, 3-sec-butoxy-tetrahydrothiophene-1,1-dioxide, 3-tert-butoxy-tetrahydrothiophene-1,1-dioxide, 3- (2-ethyl) -hexoxy-tetrahydrothiophene-1,1-dioxide, 3- (2-methoxy) -ethoxy-tetrahydrothiophene-1,1-dioxide-3- (2-ethoxy) -e
  • the process for electrochemical fluorination itself is described, inter alia, in US Pat. Nos. 2,717,871 and 2,519,983, in Houben-Weyl, Methods of Organic Chemistry, Vol. C, T. 3, pp. 42-50 and in DE- OS 2 442 106 and DE-OS 2 725 211 described in more detail.
  • the process according to the invention is carried out at a substrate concentration of 0.2 to 10 percent by weight in hydrogen fluoride, an electrolysis voltage between 4.5 and 15 V, a current density of 4-20 mA / cm 1 effective anode surface and a temperature between -20 ° C. and 50 ° C, preferably between 0 and 15 ° C, carried out.
  • the starting compounds of general formula II are dissolved in hydrogen fluoride in an amount of 0.2 to 10 percent by weight at the beginning of the electrolysis.
  • the resulting solutions conduct the electrical current.
  • hydrogen fluoride and organic substrate are replaced discontinuously or continuously depending on consumption.
  • the hydrogen formed on the cathode is largely freed of entrained hydrogen fluoride in ascending, reflux coolers charged with cooling brine and this is returned to the electrolyte cell.
  • the perfluoro raw products collect as specific heavy liquids at a low point in the electrolysis apparatus and are removed from time to time.
  • Examples of compounds prepared according to the invention are 4-oxa-3-trifluoromethyl-perfluoropentyl-1-sulfofluoride, 3-oxa-2-pentafluoroethyl-perfluorobutyl-1-sulfofluoride, 4-oxa-3-trifluoromethyl-perfluorhexyl-1-sulfofluoride, 3- Oxa-2-pentafluoroethyl-perfluoropentyl-1-sulfofluoride, 4-oxa-3,5-bis-trifluoromethyl-perfluorohexyl-1-sulfofluoride, 3-oxa-2-pentafluoroethyl-4-trifluoromethyl-perfluoropentyl-1-sulfofluoride, 4-oxa-3-trifluoromethyl-6-pentafluoroethyl-perfluorodecyl-1-sulfofluoride, 3-ox
  • the perfluorinated sulfonic acid fluorides of the general formula I can be used for numerous purposes. According to DE-OS 1 929 665, they can be converted into the tetraethylammonium salt of the respective oxaperfluorosulfonic acid. These give water a low surface tension in very low concentrations and can thus be used as a wetting and leveling agent. Alkaline or ammoniacal hydrolysis gives the analogous alkali and ammonium salts, which are also used as surfactants.
  • the additive product is prepared from ⁇ 3-dihydrothiophene-1,1-dioxide and n-butanol.
  • the resulting 3-n-butoxy-tetrahydrothiophene-1,1-dioxide boils at 123-130 ° C and 10 mbar.
  • 3-Methoxy-tetrahydrothiophene-1,1-dioxide is produced in accordance with DE-PS 682 079.
  • the compound is electrochemically fluorinated analogously to Example 1.
  • 11 kg of starting product provide 11.6 kg of a 1: 4 substance mixture of 4-oxa-3-trifluoromethyl-perfluoropentyl-1-sulfofluoride and 3-oxa-2-pentafluoroethyl-perfluorobutyl-1-sulfofluoride. This corresponds to a yield of 44%.
  • the starting compound is prepared according to DE-PS 682 079 and electrofluorinated analogously to Example 1. 16 kg of the starting product provide 11.2 kg of a 1: 4 mixture of 4,7-dioxa-3-trifluoromethyl-perfluorooctyl-1-sulfofluoride and 3,6-dioxa-2-pentafluoroethyl-per-fluorheptyl-1-sulfofluoride. This corresponds to a yield of 28 percent.

Abstract

Die Erfindung betrifft perfluorierte Sulfonsäurefluoride der allgemeinen Formel <IMAGE> in denen X, Y und Z unabhängig voneinander für F, einen Perfluoralkylrest mit 1 - 8 C-Atomen, in dem gegebenenfalls eine oder mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können, wobei die Sauerstoffatome durch mindestens eine CF2-Gruppe voneinander getrennt sind, einen gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest mit 5 - 12 C-Atomen, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können. X und Y gemeinsam für einen gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff substituiert sein können, Rf unabhängig für F oder einen Perfluoralkylrest mit 1 - 3 C-Atomen steht, und n und m für die Zahlen 0 oder 1 stehen. Die Erfindung betrifft ferner ein Verfahren zur Herstellung der genannten perfluorierten Sulfonsäurefluoride.The invention relates to perfluorinated sulfonic acid fluorides of the general formula <IMAGE> in which X, Y and Z independently of one another for F, a perfluoroalkyl radical having 1-8 C atoms, in which one or more CF2 groups can optionally be replaced by oxygen, the Oxygen atoms are separated from one another by at least one CF2 group, an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical having 5 to 12 carbon atoms, in which one or more CF2 groups can be replaced by oxygen. X and Y together represent an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical, in which one or more CF2 groups can be substituted by oxygen, Rf independently represents F or a perfluoroalkyl radical with 1-3 C atoms, and n and m represent the numbers 0 or 1 stand. The invention further relates to a process for the preparation of said perfluorinated sulfonic acid fluorides.

Description

Die Erfindung betrifft perfluorierte Sulfonsäurefluoride der allgemeinen Formel

Figure imgb0001
in denen X, Y und Z unabhängig voneinander für F, einen Perfluoralkylrest mit 1 - 8 C-Atomen, in dem gegebenenfalls eine oder.mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können, wobei die Sauerstoffatome durch mindestens eineCF2-Gruppe voneinander getrennt sind, einen gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest mit 5 - 12 C-Atomen, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können,The invention relates to perfluorinated sulfonic acid fluorides of the general formula
Figure imgb0001
 in which X, Y and Z independently of one another represent F, a perfluoroalkyl radical having 1-8 C atoms, in which one or more CF 2 groups can optionally be replaced by oxygen, the oxygen atoms being separated from one another by at least one CF2 group an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical with 5 to 12 carbon atoms, in which one or more CF 2 groups can be replaced by oxygen,

X und Y gemeinsam für einen gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff substituiert sein können, Rf unabhängig für F oder einen Perfluoralkylrest mit 1 - 3 C-Atomen steht, und n und m für die Zahlen 0 oder 1 stehen. Die Erfindung be-- trifft ferner ein Verfahren zur Herstellung der genannten perfluorierten Sulfonsäurefluoride.X and Y together for an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical in which one or more CF 2 groups can be substituted by oxygen, R f independently represents F or a perfluoroalkyl radical having 1 to 3 carbon atoms, and n and m represent the numbers 0 or 1. The invention further relates to a process for the preparation of said perfluorinated sulfonic acid fluorides.

Bei der herkömmlichen Elektrofluorierung von Alkylsulfonsäurehalogeniden zu Perfluoralkylsulfonsäurefluoriden werden mit steigender Kettenlänge niedrigere Ausbeuten erhalten, die ihre Ursache in Spaltungen oder Umlagerungen des Kohlenstoffgerüsts sowie Polymerisation unter Schlammbildung haben. Besonders bei den technisch interessanten längerkettigen Perfluoralkylsulfonylfluoriden führt das Verfahren nur zu unbefriedigenden Ausbeuten (vgl. z.B.: J. Chem. Soc., 1957, 2640). Hinzu kommt, daß die Ausgangsverbindungen, Alkyl-l-sulfonsäurefluoride oder -chloride, nur durch mehrstufige, aufwendige und zu zahlreichen nicht nutzbaren Nebenprodukten führende Verfahren zugänglich sind. So führt z.B. die Synthese von C8H17SO2F zu mindestens der 1,7-fachen Menge an NaCl, das entweder über das Abwasser abgeführt oder mit aufwendigen Reinigungsverfahren beseitigt werden muß.In the conventional electrofluorination of alkylsulfonic acid halides to perfluoroalkylsulfonic acid fluorides, lower yields are obtained with increasing chain length, which are due to cleavages or rearrangements of the carbon skeleton and polymerization with sludge formation. Particularly in the case of the technically interesting longer-chain perfluoroalkylsulfonyl fluorides, the process leads to unsatisfactory yields (see, for example: J. Chem. Soc., 1957, 2640). In addition, the starting compounds, alkyl-l-sulfonic acid fluorides or chlorides, can only be obtained by multi-stage, complex and leading to numerous useless by-products. For example, the synthesis of C 8 H 17 SO 2 F leads to at least 1.7 times the amount of NaCl, which either has to be discharged via the wastewater or has to be removed using complex cleaning processes.

Es liegt daher der Erfindung die Aufgabe zugrunde, in einem verbesserten Verfahren neue, mindestens ein Sauerstoffatom in Etherfunktion enthaltende perfluorierte Sulfonsäurefluoride zu synthetisieren, nach dem die gewünschten Verbindungen in vergleichbar mit den bisherigen Verfahren guter Ausbeute aus leicht zugänglichen Ausgangsverbindungen erhalten werden.It is therefore an object of the invention to provide, in an improved process, new per containing at least one oxygen atom in ether function To synthesize fluorinated sulfonic acid fluorides, after which the desired compounds are obtained in comparable yields from the readily available starting compounds in a good yield comparable to the previous processes.

Die Lösung dieser Aufgabe wurde überraschenderweise in dem Weg gefunden, die nach DE-PS 682 079 leicht zugänglichen Additionsprodukte von primären, sekundären und tertiären Alkoholen an Δ 3-Dihydrothiophen-1,1-dioxide (wie z.B. Sulfolen) der allgemeinen Formel

Figure imgb0002
in der X', Y' und Z' unabhängig voneinander für H, einen Alkylrest mit 1 - 8 C-Atomen, in dem eine oder mehrere CH2-Gruppen durch Sauerstoff substituiert sein können, wobei die Sauerstoffatome durch mindestens eine CH2-Gruppe voneinander getrennt sind, einen gegebenenfalls alkylsubstituierten Cycloalkylrest mit 5 - 12 C-Atomen, in dem eine oder merhere der CH2-Gruppen durch Sauerstoff ersetzt sein können,The solution to this problem was surprisingly found in the way, according to DE-PS 682 079 easily accessible addition products of primary, secondary and tertiary alcohols with Δ 3-dihydrothiophene-1,1-dioxide (such as sulfolene) of the general formula
Figure imgb0002
 in which X ', Y' and Z 'independently of one another represent H, an alkyl radical having 1-8 C atoms, in which one or more CH 2 groups can be substituted by oxygen, the oxygen atoms being substituted by at least one CH 2 group are separated from one another, an optionally alkyl-substituted cycloalkyl radical having 5 to 12 carbon atoms, in which one or more of the CH 2 groups can be replaced by oxygen,

X' und Y' gemeinsam für einen gegebenenfalls alkylsubstituierten Cycloalkylrest, in dem eine oder mehrere CH2-Gruppen durch Sauerstoff substituiert sein können und R unabhängig für H oder einen Alkylrest mit 1 bis 3 C-Atomen steht, der elektrochemischen Fluorierung zu unterwerfen.X 'and Y' together for an optionally alkyl-substituted cycloalkyl radical in which one or several CH 2 groups can be substituted by oxygen and R independently represents H or an alkyl radical having 1 to 3 C atoms to be subjected to the electrochemical fluorination.

Nach GB-PS 1 099 240 und BE-PS 747 306 ist die elektrochemische Fluorierung von cyclischen Sulfonen zu Perfluoralkylsulfonylfluoriden an sich bekannt. Völlig überraschend ist jedoch, daß auch diese substituierten Sulfone ohne Spaltung der Etherbindung zu perfluoralkylsubstituierten offenkettigen Sulfonylfluoriden elektrofluoriert werden können, da andererseits eine der Schwefel-Kohlenstoff-Bindung fluorierend gespalten wird.According to GB-PS 1 099 240 and BE-PS 747 306, the electrochemical fluorination of cyclic sulfones to perfluoroalkylsulfonyl fluorides is known per se. However, it is completely surprising that these substituted sulfones can also be electrofluorinated without cleavage of the ether bond to perfluoroalkyl-substituted open-chain sulfonyl fluorides, since on the other hand one of the sulfur-carbon bonds is cleaved in a fluorine manner.

Die bevorzugte Klasse an Ausgangsverbindungen der allgemeinen Formel II sind diejenigen, in denen X', Y' und Z' für H, X' und Y' für einen kurzkettigen Alkylrest mit 1 - 6 C-Atomen, in denen gegebenenfalls maximal zwei CH2-Gruppen durch Sauerstoff substituiert sind oder X' und Y' gemeinsam für einen gegebenenfalls alkylsubstituierten Cycloalkylrest mit 5 - 8 Kohlenstoffatomen, wobei einzelne CH2-Gruppen durch Sauestoff ersetzt sein können, sowie R unabhängig für H oder eine Methylgruppe stehen.The preferred class of starting compounds of the general formula II are those in which X ', Y' and Z 'for H, X' and Y 'for a short-chain alkyl radical having 1-6 C atoms, in which a maximum of two CH 2 - Groups are substituted by oxygen or X 'and Y' together represent an optionally alkyl-substituted cycloalkyl radical with 5-8 carbon atoms, where individual CH 2 groups can be replaced by oxygen, and R independently represents H or a methyl group.

Beispiele für die bei dem erfindungsgemäßen Verfahren benutzten Ausgangsverbindungen sind 3-Methoxy- tetrahydrothiophen-1,1-dioxid, 3-Ethoxy-tetrahydrothio- phen-1,1-dioxid, 3-n-Propoxy-tetrahydrothiophen-1,1-dioxid, 3-i-Propoxy-tetrahydrothiophen-1,1-dioxid, 3-n-Butoxy-tetrahydrothiophen-1,1-dioxid, 3-sec-Butoxy-tetrahydrothiophen-1,1-dioxid, 3-tert.-Butoxy- tetrahydrothiophen-1,1-dioxid, 3-(2-Ethyl)-hexoxy- tetrahydrothiophen-1,1-dioxid, 3-(2-Methoxy)-ethoxy- tetrahydrothiophen-1,1-dioxid-3-(2-Ethoxy)-ethoxy- tetrahydrothiophen-1,1-dioxid, 3-Cyclohexoxy-tetra- hydrothiophen-1,1-dioxid, 3-(4-Methyl)-cyclohexoxy- tetrahydrothiophen-1,1-dioxid, 3-(4-Methoxy)-cyclo- hexoxy-tetrahydrothiophen-1,1-dioxid, 3-Methyl-4-methoxy- tetrahydrothiophen-1,1-dioxid, 2-Ethyl-3-methoxy- tetrahydrothiophen-1,1-dioxid, 3-Methyl-3-methoxy- tetrahydrothiophen-1,1-dioxid und 2-Methyl-3-methoxy- tetrahydrothiophen-1,1-dioxid.Examples of the starting compounds used in the process according to the invention are 3-methoxy tetrahydrothiophene-1,1-dioxide, 3-ethoxy-tetrahydrothiophene-1,1-dioxide, 3-n-propoxy-tetrahydrothiophene-1,1-dioxide, 3-i-propoxy-tetrahydrothiophene-1,1-dioxide, 3-n-butoxy-tetrahydrothiophene-1,1-dioxide, 3-sec-butoxy-tetrahydrothiophene-1,1-dioxide, 3-tert-butoxy-tetrahydrothiophene-1,1-dioxide, 3- (2-ethyl) -hexoxy-tetrahydrothiophene-1,1-dioxide, 3- (2-methoxy) -ethoxy-tetrahydrothiophene-1,1-dioxide-3- (2-ethoxy) -ethoxy-tetrahydrothiophene-1,1-dioxide, 3-cyclohexoxy -tetra-hydrothiophene-1,1-dioxide, 3- (4-methyl) -cyclohexoxy-tetrahydrothiophene-1,1-dioxide, 3- (4-methoxy) -cyclo-hexoxy-tetrahydrothiophene-1,1-dioxide, 3 -Methyl-4-methoxy-tetrahydrothiophene-1,1-dioxide, 2-ethyl-3-methoxy-tetrahydrothiophene-1,1-dioxide, 3-methyl-3-methoxy-tetrahydrothiophene-1,1-dioxide and 2-methyl -3-methoxy-tetrahydrothiophene-1,1-dioxide.

Das Verfahren zur elektrochemischen Fluorierung selbst wird unter anderen in den US-Patentschriften 2 717 871 und 2 519 983, in Houben-Weyl, Methoden der organischen Chemie, Bd. C, T. 3, S. 42 - 50 und in den DE-OS 2 442 106 sowie DE-OS 2 725 211 näher beschrieben. Das erfindungsgemäße Verfahren wird bei einer Substratkonzentration von 0,2 bis 10 Gewichtsprozent in Fluorwasserstoff, einer Elektrolysespannung zwischen 4,5 und 15 V, einer Stromdichte von 4 - 20 mA/cml wirksamer Anodenfläche sowie einer Temperatur zwischen -20°C und 50°C, bevorzugt zwischen 0 und 15°C, durchgeführt.The process for electrochemical fluorination itself is described, inter alia, in US Pat. Nos. 2,717,871 and 2,519,983, in Houben-Weyl, Methods of Organic Chemistry, Vol. C, T. 3, pp. 42-50 and in DE- OS 2 442 106 and DE-OS 2 725 211 described in more detail. The process according to the invention is carried out at a substrate concentration of 0.2 to 10 percent by weight in hydrogen fluoride, an electrolysis voltage between 4.5 and 15 V, a current density of 4-20 mA / cm 1 effective anode surface and a temperature between -20 ° C. and 50 ° C, preferably between 0 and 15 ° C, carried out.

Die Ausgangsverbindungen der allgemeinen Formel II werden zu Beginn der Elektrolyse in Fluorwasserstoff in einer Menge von 0,2 bis 10 Gewichtsprozent gelöst. Die resultierenden Lösungen leiten den elektrischen Strom. Während der Elektrolyse werden Fluorwasserstoff und organisches Substrat diskontinuierlich oder kontinuierlich je nach Verbrauch ersetzt. Der kathodisch gebildete Wasserstoff wird an aufsteigenden, mit Kühlsole beschickten Rückflußkühlern weitgehend von mitgeführtem Fluorwasserstoff befreit und dieser in die Elektrolytzelle zurückgeführt. Die Perfluorrohprodukte sammeln sich als spezifisch schwere Flüssigkeiten an einer tiefliegenden Stelle der Elektrolyseapparatur und werden von Zeit zu Zeit ausgeschleust.The starting compounds of general formula II are dissolved in hydrogen fluoride in an amount of 0.2 to 10 percent by weight at the beginning of the electrolysis. The resulting solutions conduct the electrical current. During the electrolysis, hydrogen fluoride and organic substrate are replaced discontinuously or continuously depending on consumption. The hydrogen formed on the cathode is largely freed of entrained hydrogen fluoride in ascending, reflux coolers charged with cooling brine and this is returned to the electrolyte cell. The perfluoro raw products collect as specific heavy liquids at a low point in the electrolysis apparatus and are removed from time to time.

Durch die Erfindung wird erreicht, daß perfluorierte Sulfonsäurefluoride der allgemeinen Formel I

Figure imgb0003
wobei X, Y, Z, Rf sowie n und m die vorstehend genannten Bedeutungen haben, in, vergleichsweise zur Herstellung von Perfluoralkylsulfonylfluoriden gleicher Kettenlänge, guten Ausbeuten entstehen. Beispiele für erfindungsgemäß hergestellte Verbindungen sind 4-Oxa-3-trifluormethyl-perfluorpentyl-1-sulfofluorid, 3-Oxa-2-pentafluorethyl-perfluorbutyl-1-sulfofluorid, 4-Oxa-3-trifluormethyl-perfluorhexyl-1-sulfofluorid, 3-Oxa-2-pentafluorethyl-perfluorpentyl-1-sulfofluorid, 4-Oxa-3,5-bis-trifluormethyl-perfluorhexyl-1-sulfo- fluorid, 3-Oxa-2-pentafluorethyl-4-trifluormethyl- perfluorpentyl-1-sulfofluorid, 4-Oxa-3-trifluormethyl-6-pentafluorethyl-perfluordecyl-1-sulfo- fluorid, 3-Oxa-2,5-bis-pentafluorethyl-perfluornonyl-1-sulfofluorid, 4,7-Dioxa-3-trifluormethyl-perfluor- octyl-1-sulfofluorid, 3,6-Dioxa-2-pentafluorethyl- perfluorheptyl-1-sulfofluorid, 4-Oxa-3-trifluormethyl-4-perfluorcyclohexyl-perfluorbutyl-1-sulfofluorid, 3-Oxa-2-pentafluorethyl-3-perfluorcyclohexyl-per- fluorpropyl-1-sulfofluorid, 4-Oxa-3-pentafluorethyl- perfluorpentyl-1-sulfofluorid und 3-Oxa-1-trifluormethyl-2-pentafluorethyl-perfluorbutyl-1-sulfofluorid.It is achieved by the invention that perfluorinated sulfonic acid fluorides of the general formula I
Figure imgb0003
 where X, Y, Z, R f and n and m have the meanings given above, in comparison to the preparation of perfluoroalkylsulfonyl fluorides of the same chain length, good yields arise. Examples of compounds prepared according to the invention are 4-oxa-3-trifluoromethyl-perfluoropentyl-1-sulfofluoride, 3-oxa-2-pentafluoroethyl-perfluorobutyl-1-sulfofluoride, 4-oxa-3-trifluoromethyl-perfluorhexyl-1-sulfofluoride, 3- Oxa-2-pentafluoroethyl-perfluoropentyl-1-sulfofluoride, 4-oxa-3,5-bis-trifluoromethyl-perfluorohexyl-1-sulfofluoride, 3-oxa-2-pentafluoroethyl-4-trifluoromethyl-perfluoropentyl-1-sulfofluoride, 4-oxa-3-trifluoromethyl-6-pentafluoroethyl-perfluorodecyl-1-sulfofluoride, 3-oxa-2,5-bis-pentafluoroethyl-perfluorononyl-1-sulfofluoride, 4,7-dioxa-3-trifluoromethyl-perfluoro- octyl-1-sulfofluoride, 3,6-dioxa-2-pentafluoroethyl-perfluoroheptyl-1-sulfofluoride, 4-oxa-3-trifluoromethyl-4-perfluorocyclohexyl-perfluorobutyl-1-sulfofluoride, 3-oxa-2-pentafluorethyl-3- perfluorocyclohexyl-per-fluoropropyl-1-sulfofluoride, 4-oxa-3-pentafluoroethyl-perfluoropentyl-1-sulfofluoride and 3-oxa-1-trifluoromethyl-2-pentafluoroethyl-perfluorobutyl-1-sulfofluoride.

Nach 19F-NMR- und gaschromatographischen Untersuchungen werden die isomeren Verbindungen I mit m=1, n=0 und m=0, n=1 aus ein und derselben Ausgangsverbindung II etwa in einem Gewichtsverhältnis wie 1 : 4 erhalten.After 19 FN M R and gas chromatographic studies, the isomeric compounds I with m = 1 , n = 0 and m = 0 , n = 1 are obtained from one and the same starting compound II in a weight ratio of approximately 1: 4.

Die perfluorierten Sulfonsäurefluoride der allgemeinen Formel I sind für zahlreiche Zwecke nutzbar. So lassen sie sich gemäß DE-OS 1 929 665 in das Tetraethylammoniumsalz der jeweiligen Oxaperfluorsulfonsäure überführen. Diese verleihen Wasser in sehr geringen Einsatzkonzentrationen eine niedrige Oberflächenspannung und lassen sich damit als Netz-und Verlaufsmittel nutzen. Durch alkalische oder ammonialkalische Hydrolyse erhält man die analogen Alkali- und Ammoniumsalze, die ebenfalls als Tenside eingesetzt werden. Die Umsetzung mit wasserfreiem Ammoniak und primären Aminen führt zu Oxaperfluoralkylsulfonamiden, die als Ausgangsverbindungen für die schmutzabweisende sowie hydro- und oleophobe Ausrüstung von Leder-, Papier- und Textiloberflächen dienen.The perfluorinated sulfonic acid fluorides of the general formula I can be used for numerous purposes. According to DE-OS 1 929 665, they can be converted into the tetraethylammonium salt of the respective oxaperfluorosulfonic acid. These give water a low surface tension in very low concentrations and can thus be used as a wetting and leveling agent. Alkaline or ammoniacal hydrolysis gives the analogous alkali and ammonium salts, which are also used as surfactants. The reaction with anhydrous ammonia and primary amines leads to oxaperfluoroalkylsulfonamides, which serve as starting compounds for the dirt-repellent and hydro- and oleophobic finishing of leather, paper and textile surfaces.

Die folgenden Beispiele erläutern die Erfindung, ohne sie jedoch auf diese zu begrenzen.The following examples illustrate the invention, but without restricting it to them.

Beispiel 1example 1 Elektrochemische Fluorierung von 3-n-Butoxy-tetra- hydrothiophen-1,1-dioxidElectrochemical fluorination of 3-n-butoxy-tetra-hydrothiophene-1,1-dioxide

Nach DE-PS 682 079 wird das Additonsprodukt aus Δ3-Dihydrothiophen-1,1-dioxid und n-Butanol hergestellt. Das resultierende 3-n-Butoxy-tetrahydrothio- phen-1,1-dioxid siedet bei 123-130°C und 10 mbar.According to DE-PS 682 079, the additive product is prepared from Δ3-dihydrothiophene-1,1-dioxide and n-butanol. The resulting 3-n-butoxy-tetrahydrothiophene-1,1-dioxide boils at 123-130 ° C and 10 mbar.

Dieses wird in einer in DE-OS 2 715 211 näher beschriebenen Apparatur in einer anfänglichen Konzentration von 2 Gewichtsprozent in Fluorwasserstoff gelöst und bei einer Stromdichte von 4 - 20 mA/cm2 Anodenfläche über 35 Tage elektrolysiert. Fluorwasserstoff wird je nach Verbrauch, 3-n-Butoxy- tetrahydrothiophen-1,1-dioxid je nach Stromaufnahme nachdosiert. Von Zeit zu Zeit wird das Perfluorrohprodukt aus dem Elektrolytsystem abgelassen. Insgesamt werden 27,9 kg Ausgangsprodukt eingesetzt und 40,6 kg Perfluorrohprodukt gewonnen.This is dissolved in an initial concentration of 2% by weight in hydrogen fluoride in an apparatus described in more detail in DE-OS 2 715 211 and electrolyzed at a current density of 4-20 mA / cm 2 anode surface over 35 days. Depending on consumption, hydrogen fluoride is added, 3-n-butoxy-tetrahydrothiophene-1,1-dioxide depending on the power consumption. From time to time, the perfluoro crude product is drained from the electrolyte system. A total of 27.9 kg of starting product are used and 40.6 kg of perfluoro crude product are obtained.

Eine Fraktionierung des Perfluorrohproduktes liefert 23,3 kg eines 1 : 4 Gemisches, das aus 4-Oxa-3-trifluormethyl-perfluoroctyl-1-sulfofluorid sowie 3-Oxa-2-pentafluorethyl-perfluorheptyl-1-sulfo- fluorid besteht.Fractionation of the perfluoro crude product gives 23.3 kg of a 1: 4 mixture consisting of 4-oxa-3-trifluoromethyl-perfluorooctyl-1-sulfofluoride and 3-oxa-2-pentafluoroethyl-perfluoroheptyl-1-sulfofluoride.

Die Ausbeute bezogen auf eingesetztes 3-n-Butoxy- tetrahydrothiophen-1,1-dioxid beträgt 31 Prozent.The yield based on 3-n-butoxy-tetrahydrothiophene-1,1-dioxide is 31 percent.

Beispiel 2Example 2 Elektrochemische Fluorierung von 3-Isopropoxy-tetra- hydrothiophen-1,1-dioxidElectrochemical fluorination of 3-isopropoxy-tetra-hydrothiophene-1,1-dioxide

Nach DE-PS 682 079 wird 3-Isopropoxy-tetrahydrothiophen-1,1-dioxid synthetisiert und analog Beispiel 1 elektrolysiert. Bei Einsatz von 30 kg der Ausgangsverbindungen erhält man 28,4 kg eines 1 : 4 Gemisches an 4-Oxa-3,5-bis-trifluormethyl-perfluorhexyl-1-sulfofluorid und 3-Oxa-2-pentafluorethyl-4-trifluormethyl-perfluorpentyl-1-sulfofluorid. Dies entspricht einer Ausbeute von 36 Prozent bezogen auf eingesetztes Ausgangsprodukt.According to DE-PS 682 079, 3-isopropoxy-tetrahydrothiophene-1,1-dioxide is synthesized and electrolyzed as in Example 1. When 30 kg of the starting compounds are used, 28.4 kg of a 1: 4 mixture of 4-oxa-3,5-bis-trifluoromethyl-perfluorohexyl-1-sulfofluoride and 3-oxa-2-pentafluoroethyl-4-trifluoromethyl-perfluoropentyl are obtained -1-sulfofluoride. This corresponds to a yield of 36 percent based on the starting product used.

Beispiel 3Example 3 Elektrochemische Fluorierung von 3-Methoxy-tetra- hydrothiophen-1,1-dioxidElectrochemical fluorination of 3-methoxy-tetra-hydrothiophene-1,1-dioxide

Die Herstellung von 3-Methoxy-tetrahydrothiophen-1,1-dioxid erfolgt gemäß DE-PS 682 079. Die Verbindung wird analog Beispiel 1 elektrochemisch fluoriert. 11 kg Ausgangsprodukt liefern 11,6 kg eines 1 : 4 Substanzgemisches an 4-Oxa-3-trifluormethyl-perfluor- pentyl-1-sulfofluorid und 3-Oxa-2-pentafluorethyl- perfluorbutyl-1-sulfofluorid. Dies entspricht einer Ausbeute von 44 %.3-Methoxy-tetrahydrothiophene-1,1-dioxide is produced in accordance with DE-PS 682 079. The compound is electrochemically fluorinated analogously to Example 1. 11 kg of starting product provide 11.6 kg of a 1: 4 substance mixture of 4-oxa-3-trifluoromethyl-perfluoropentyl-1-sulfofluoride and 3-oxa-2-pentafluoroethyl-perfluorobutyl-1-sulfofluoride. This corresponds to a yield of 44%.

Beispiel 4Example 4 Elektrochemische Fluorierung von 3-(2-Methoxy)-ethoxy- tetrahydrothiophen-1,1-dioxidElectrochemical fluorination of 3- (2-methoxy) -ethoxy-tetrahydrothiophene-1,1-dioxide

Die Ausgangsverbindung wird nach DE-PS 682 079 hergestellt und analog Beispiel 1 elektrofluoriert. 16 kg des Ausgangsproduktes liefern 11,2 kg eines 1 : 4 Gemisches 4,7-Dioxa-3-trifluormethyl-perfluoroctyl-1-sulfofluorid und 3,6-Dioxa-2-pentafluorethyl-per- fluorheptyl-1-sulfofluorid. Dies entspricht einer Ausbeute von 28 Prozent.The starting compound is prepared according to DE-PS 682 079 and electrofluorinated analogously to Example 1. 16 kg of the starting product provide 11.2 kg of a 1: 4 mixture of 4,7-dioxa-3-trifluoromethyl-perfluorooctyl-1-sulfofluoride and 3,6-dioxa-2-pentafluoroethyl-per-fluorheptyl-1-sulfofluoride. This corresponds to a yield of 28 percent.

Beispiel 5Example 5 Elektrochemische Fluorierung von 3-Cyclohexoxy-tetra- hydrothiophen-1,1-dioxidElectrochemical fluorination of 3-cyclohexoxy-tetra-hydrothiophene-1,1-dioxide

Nach DE-PS 682 079 wird 3-Cyclohexoxy-tetrahydrothiophen-1,1-dioxid hergestellt und analog Beispiel 1 elektrochemisch fluoriert. 14 kg des Ausgangsproduktes liefern 8,2 kg eines 1 : 4 Gemisches an 4-Oxa-3-trifluormethyl-4-perfluorcyclohexyl-perfluorbutyl-1-sulfofluorid und 3-Oxa-2-pentafluorethyl-3-perfluorcyclohexyl-perfluor- propyl-1-sulfofluorid. Die Ausbeute bezogen auf eingesetztes Produkt beträgt 22 Prozent.According to DE-PS 682 079, 3-cyclohexoxy-tetrahydrothiophene-1,1-dioxide is produced and, analogously to Example 1, fluorinated electrochemically. 14 kg of the starting product provide 8.2 kg of a 1: 4 mixture of 4-oxa-3-trifluoromethyl-4-perfluorocyclohexyl-perfluorobutyl-1-sulfofluoride and 3-oxa-2-pentafluoroethyl-3-perfluorocyclohexyl-perfluoropropyl-1 -sulfofluoride. The yield based on the product used is 22 percent.

Claims (6)

1) Perfluorierte Sulfonsäurefluoride der allgemeinen Formel
Figure imgb0004
wobei X, Y und Z unabhängig voneinander für F, einen Perfluoralkylrest mit 1 bis 8 C-Atomen in dem gegebenenfalls eine oder mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können, wobei die Sauerstoffatome durch mindestens eine CF2-Gruppe voneinander getrennt sind, einem gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest mit 5 - 12 C-Atomen, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff ersetzt sein können, X und Y gemeinsam für einen gegebenenfalls perfluoralkylsubstituierten Cycloperfluoralkylrest, in dem eine oder mehrere CF2-Gruppen durch Sauerstoff sein könne, Rf unabhängig für F oder einen Perfluoralkylrest mit 1 - 3 C-Atomen und n sowie m für die Zahlen 0 oder 1 stehen. 1) Perfluorinated sulfonic acid fluorides of the general formula
Figure imgb0004
 in which X, Y and Z independently of one another for F, a perfluoroalkyl radical having 1 to 8 C atoms in which one or more CF 2 groups can optionally be replaced by oxygen, the oxygen atoms being separated from one another by at least one CF 2 group, one optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical having 5 to 12 carbon atoms, in which one or more CF 2 groups can be replaced by oxygen, X and Y together represent an optionally perfluoroalkyl-substituted cycloperfluoroalkyl radical in which one or more CF 2 groups may be through oxygen, R f independently represent F or a perfluoroalkyl radical with 1 to 3 C atoms and n and m stand for the numbers 0 or 1 . 2) Verfahren zur Herstellung perfluorierter Sulfonsäurefluoride gemäß Anspruch 1, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel
Figure imgb0005
in der X', Y' und Z' unabhängig voneinander für H, einen Alkylrest mit 1 - 8 C-Atomen, in dem eine oder mehrere CH2-Gruppen durch Sauerstoff substituiert sein können, wobei die Sauerstoffatome durch mindestens eine CH2-Gruppe voneinander getrennt sind, einen gegebenenfalls alkylsubstituierten Cycloalkylrest mit 5 - 12 C-Atomen, in dem eine oder mehrere der CH2-Gruppen durch Sauerstoff ersetzt sein können, X' und Y' gemeinsam für einen gegebenenfalls alkylsubstituierten Cycloalkylrest, in dem eine oder mehrere CH2-Gruppen durch Sauerstoff substituiert sein können, R unabhängig für.H oder einen Alkylrest mit 1 bis 3 C-Atomen stehen, der elektrochemischen Fluorierung unterwirft.2) Process for the preparation of perfluorinated sulfonic acid fluorides according to claim 1, characterized in that compounds of the general formula
Figure imgb0005
 in which X ', Y' and Z 'independently of one another represent H, an alkyl radical having 1-8 C atoms, in which one or more CH 2 groups can be substituted by oxygen, the oxygen atoms being substituted by at least one CH 2 group are separated from one another, an optionally alkyl-substituted cycloalkyl radical having 5 to 12 carbon atoms, in which one or more of the CH 2 groups can be replaced by oxygen, X 'and Y' together for an optionally alkyl-substituted cycloalkyl radical in which one or more CH 2 groups can be substituted by oxygen, R is independently H or an alkyl radical having 1 to 3 carbon atoms, which is subject to electrochemical fluorination. 3) Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß die Elektrofluorierung bei Temperaturen zwischen etwa -20°C und etwa 50°C durchgeführt wird.3) Method according to claim 2, characterized in that the electrofluorination is carried out at temperatures between about -20 ° C and about 50 ° C. 4) Verfahren nach einem der Ansprüche 2 oder 3, dadurch gekennzeichnet, daß die Elektrofluorierung bei einer Stromdichte von 4 bis 20 mA/cm2 wirksamer Anodenfläche durchgeführt wird.4) Method according to one of claims 2 or 3, characterized in that the electrofluorination is carried out at a current density of 4 to 20 mA / cm 2 effective anode surface. 5) Verwendung von perfluorierten Sulfonsäurefluoriden gemäß Anspruch 1 zur Herstellung oberflächenaktiver Substanzen.5) Use of perfluorinated sulfonic acid fluorides according to claim 1 for the production of surface-active substances. 6) Verwendung von perfluorierten Sulfonsäurefluoriden gemäß Anspruch 1 zur Herstellung von Ausgangsverbindungen zur hydro- und oleophoben Ausrüstung von Oberflächen.6) Use of perfluorinated sulfonic acid fluorides according to claim 1 for the preparation of starting compounds for the hydro- and oleophobic finishing of surfaces.
EP81109563A 1980-11-18 1981-11-07 Process for the preparation of fluorides of perfluorinate sulphonic acids Withdrawn EP0052319A1 (en)

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EP2484662A1 (en) * 2009-09-29 2012-08-08 Mitsubishi Materials Corporation Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof

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JP5558067B2 (en) * 2008-10-15 2014-07-23 三菱マテリアル株式会社 Method for producing perfluorosulfonic acid having an ether structure and derivatives thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivatives thereof
CN113698796B (en) * 2020-08-26 2022-03-22 中国石油大学(北京) Super-amphiphobic agent for high-temperature-resistant water-based drilling fluid

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